Polyether urethane foam

ABSTRACT

WHAT IS CLAIMED IS: 1. AN ARALKYL MODIFIED SILOXANE OIL HAVING THE AVERAGE FORMULA   (X)2R3-ZSIO(R2SIO)X((X)(R)SIO)YSIR3-ZXZ   WHEREIN X HAS A VALUE OF 2 TO 8 INCLUSIVE; Y HAS A VALUE OF 0 TO 6 INCLUSIVE; Z HAS A VALUE OF 0 TO 1 INCLUSIVE; R IS A LOWER ALKYL OR PHENYL RADICAL; AND X IS AN ARALKYL RADICAL OF THE FORMULA   -CNH2N-C6H5   WHRE A HAS A VALUE OF 2 OR 3; SAID SILOXANE CONTAINING AT LAST ONE OF SAID ARALKYL RADICALS AND HAVING A VISCOSITY IN THE RANGE OF ABOUT 4 TO ABOUT 40 CENTISTOKES AT 25* C.

United States Patent 3,839,384 POLYETHER URETHANE FOAM Edward LewisMorehouse, New City, N.Y., assignor to Union Carbide Corporation, NewYork, N .Y. No Drawing. Filed Nov. 13, 1972, Ser. No. 305,713 Int. Cl.C07f 7/08 U.S. Cl. 260-448.2 R 14 Claims ABSTRACT OF THE DISCLOSURE Aprocess for producing high resilience polyether urethane foam using anaralkyl modified siloxane oil; the foams derived therefrom; asolvent-solution of said siloxane oil; and aralkyl modified siloxaneoils per se.

BACKGROUND OF THE INVENTION This invention relates to high resiliencepolyurethane foams and more particularly to the use of certainorganosilicon surfactants in the production of such foams.

Basically such high resilience foams are produced by the reaction ofhighly primary hydroxyl-capped, high molecular Weight polyols withorganic isocyanates and water. High resilience polyurethane foams aredistinguishable in part from conventional hot cure polyurethane foams bythe use of such polyols and the fact that high resilience polyurethanefoams require little or no oven curing and thus are often referred to ascold cure foams. Such foams are extremely desirable for cushioningapplications because of their excellent physical properties, e.g. veryhigh foam resiliency, low flammability, opencelled structure, low flexfatigue (long life) and high SAC factors (load bearing properties).

Because of the high reactivity of high resilience foam ingredients andtheir rapid buildup of gel strength, sometimes the foam can be obtainedwithout a surfactant, however such foams typically have very irregularcell structure as particularly evidenced by surface voids and thediscovery of a proper surfactant agent to help control cell structurehas remained a major problem in the art.

Attempts to solve this problem with surfactants generally employed inthe stabilization of hot cure polyurethane foam have not provensatisfactory because such surfactants tend to overstabilize, causingextremely tight, shrinkaging foam. Nor is the problem corrected byreducing the concentrations of such surfactants, since at concentrationsrequired to eliminate shrinkage, the cells are no longer stabilizedsatisfactorily and the foam structure becomes irregular, coarse andcontains surface voids.

The use of low viscosity d-imethylsilicone oils as stabilizers for highresilience foams also has various disadvantages. For example, at lowconcentrations they create metering and pumping problems in theprocessing of the foam, while at higher concentrations these oilsadversely affect the physical properties of the foam. Solvents for suchdimethylsiloxane oils that are non-reactive with the foam ingredientse.g. alkanes, hexamethyldisiloxane, and the like, can adversely alfectthe foams physical properties in proportion to their concentration andgenerally create flammability hazards. Furthermore isocyanate reactivediluents, such as polyether triols and the like which do notsignificantly change the foams properties, inasmuch as they react intothe system and become part of the foam structure, are not satisfactorysolvents for dimethylsilicone oils, since not enough oil can bedissolved to provide foam stabilization at practical solutionconcentrations. High resilience foams are also adversely affected bydimethylsilicones having more than about ten dimethylsiloxy units persiloxane. For example only five or ten weight per cent of such speciesin a dimethyl silicone oil can appreciably degrade the foarns physicalproperties and even cause foam shrinkage.

Moreover, while particularly unique high resilience polyether urethanefoam can be prepared employing certain siloxane-oxyalkylene blockcopolymer surfactants as disclosed in U.S. Patent Application Ser. No.84,181 filed Oct. 26, 1970, said disclosure does not teach the use ofthe novel organosilicon surfactants employed in this invention.

SUMMARY OF THE INVENTION It has been discovered that flexible highresilience polyether urethane foam can be prepared according to theinstant invention which involves employing certain novel siloxanecopolymer surfactants as more fully defined below.

The siloxane copolymer surfactants employed in this invention have beenfound to control the cell uniformity of high resilience polyetherurethane foam Without obtaining tight foam and with little if any foamshrinkage and without causing any severe adverse effects to the foamsphysical properties, e.g. the foams resilience and its resistancetowards flammability. Moreover voids in the foam are eliminated or atleast greatly reduced by the instant invention and the cell structure ofthe foam is also much more uniform and finer than where no surfactantagent is employed. This discovery is surprising since as outlined abovenot all surfactants are suitable for use in the production of highresilience foams. Indeed even siloxane copolymers of the same typeemployed herein, but outside the scope of the instant invention, werefound to cause shrinkage of the foam.

Therefore it is an object of this invention to provide a process forproducing high resilience polyether urethane foam. It is further anobject of this invention to provide novel organosilicon surfactants foruse in said process. It is still another object of this invention toprovide novel compositions of said surfactants for use in said process.It is also another object of this invention to provide high resiliencepolyether urethane foams produced by said process. Other objects andadvantages of this invention will become readily apparent from thefollowing description and appended claims.

More particularly this invention is directed, in part, to a process forpreparing high resilience polyether urethane foam, said processcomprising foaming and reacting a reaction mixture comprising:

(I) An organic polyol selected from the group consisting of (A) apolyether triol containing at least 40 mole percent primary hydroxylgroups and having a molecular Weight from about 2,000 to about 8,000 and(B) a mixture of said polyether triol and other polyethers having anaverage of at least two hydroxyl groups, said polyether triol of saidmixture amounting to at least 40 weight percent of the total polyolcontent;

(II) An organic polyisocyanate, said organic polyol and saidpolyisocyanate being present in the mixture in a. major amount and inthe relative amount required to produce the urethane;

(III) A blowing agent in a minor amount sufficient to foam the reactionmixture;

(IV) A catalytic amount of a catalyst for the production of the urethanefrom the organic polyol and polyisocyanate; and

(V) A minor amount of an aralkyl modified siloxane having the averageformula wherein x has a value of 2 to 8 inclusive; y has a value of 0 to6 mclusive; z has a value of 0 to l inclusive; R

is a lower alkyl or phenyl radical; and X is an aralkyl radical of theformula where a has a value of 2 or 3; said siloxane containing at leastone of said aralkyl radicals and having a viscosity in the range ofabout 4 to about 40 centistokes at 25 C.

It is to be understood of course that the above process and the appendedclaims read on employing a single ingredient of the type specified orany of the various combinations of ingredient mixtures possible. Forexample, in addition to employing a single ingredient of the typesspecified, if desired, a mixture of triols, a mixture ofpolyisocyanates, a mixture of blowing agents, a mixture of catalystsand/or a mixture of siloxane oils can be employed. Likewise thetriol-polyether starting mixture could consist of a single triol and amixture of polyethers, a mixture of triols and a single polyether or amixture of two or more triols and two or more polyethers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As indicated above the aralkylmodified siloxane oils employed as the siloxane polymer surfactantstabilizers in this invention are characterized in part as containing atleast two internal dihydrocarbyl siloxy units (R SiO) and having atleast one siloxy unit having at least one aralkyl radical. It is ofcourse to be understood that the individual internal siloxy units can bethe same or different and be arranged in any order.

Accordingly the siloxane oils useful as surfactants in this inventioncontain from 2 to 8 internal dihydrocarbyl siloxy units, such asdimethylsiloxy, diethylsiloxy, dipropylsiloxy, methylethylsiloxy,methylphenylsiloxy groups, and the like. Examples of internal aralkylsiloxy units that can be present in said siloxane oils include, e.g.(phenylethyl) methylsiloxy, (phenylethyl) ethylsiloxy,(phenylpropy1)methylsiloxy groups, and the like. Illustrativeendblocking or chain terminating siloxy units of said siloxane oils aresuch terminal groups as trimethylsiloxy, triethylsiloxy,(phenylethyl)dimethylsiloxy, (phenylpropyl)dimethylsiloxy groups and thelike. Preferably R is a methyl radical. Thus illustrative of the morepreferred polymeric siloxane oils employable in the instant inventionare trimethyl end-blocked (phenylethyl) methylsiloxy-dimethylsiloxaneoils, trimethyl end-blocked (phenylpropyl) methylsiloxy-dimethylsiloxaneoils, (phenylethyl)dimethyl endblocked dimethylsiloxane oils,(phenylpropyl)dimethyl end-blocked dimethylsiloxane oils, trimethylend-blocked (phenylethyl) methylsiloxy-(phenylpropyl) methylsiloxydimethylsiloxane oils, and (phenylethyl) dimethylendblocked-(phenylethyl) methylsiloxy-dimethylsiloxane oils.

Furthermore it is considered that the above aralkyl modified siloxaneoils having a viscosity in the range of about 4 to about 40 centistokesat 25 C. employed as the surfactant stabilizers in this invention arenovel compounds, per se. The preferred siloxane oils are those having aviscosity from about to about 20 centistokes at 25 C.

Such siloxane oils can be produced by any number of conventionalreactions well known in the art, as disclosed e.g. by US. Pat. No.3,221,040. For instance they can be prepared by the equilibration ofcorresponding siloxanes using an acid or base catalyst. They can also beprepared by the platinum-catalyzed addition of e.g. styrene oralphamethylstyrene to a hydrosiloxane. In addition they can be preparedby the cohydrolysis and co-condensation of correspondingchlorosiloxanes. It is to be understood, or course, that while thesiloxane oils used in this invention can be discrete chemical compoundsthey are usually mixtures of various discrete siloxane species, due atleast in part, to the fact that the starting materials used to producethe siloxane oils are themselves usually mixtures. Thus it is to be alsounderstood that the above formula representing the siloxane oils as usedherein also encompasses the possibility of the presence of small amountsof other siloxy units, such as (alpha-phenylethyl) methyl siloxy andmethyl(hydrogen)siloxy groups, in the siloxane oils due to an incompletereaction or the nature of the starting materials used to produce thesiloxane oils. The siloxane oils employed herein may be sparged (i.e.stripped of lites) or unsparged.

The amount of active aralkyl modified siloxane oil employed as the foamstabilizer will generally fall within the range of about 0.03 to about 2parts by weight or greater, per hundred parts by weight of the organicpolyol starting material. Generally there is no commensurate advantageto using amounts of siloxane oil greater than about 2 parts by weight,while the use of amounts below 0.03 parts by weight can result in voidsin the foam. Preferably the siloxane oils are employed in amountsranging from about 0.05 to 0.5 parts by weight per 100 parts by weightof the organic polyol starting materials.

The polyhydroxyl reactants (organic polyols) employed in this inventionas the starting materials to prepare the polyurethane foams can be anypolyether triol containing at least 40 mole percent of primary hydroxylgroups and having a molecular weight from about 2,000 to about 8,000.Conversely said polyether triols can contain no more than 60 molepercent of secondary hydroxyl groups. Preferably said polyether triolscontain about 60 to mole percent of primary hydroxyl groups and have amolecular weight from about 4,000 to about 7,000.

The preferred polyether triols of this invention are polyalkyleneethertriols obtained by the chemical addition of alkylene oxides totrihydroxyl organic containing materials, such as glycerol;1,2,6-hexanetriol; 1,1-trimethylolethane; l,l,1-trimethylolpropane;3-(2-hydroxyethoxy)- 1,2-propanediol;3-(Z-hydroxypropoxy)-1,2-propanediol; 2,4-dimethyl 2(Z-hydroxyethoxy)methylpentanediol- 1,5; 1,1,1 tris[(2 hydroxyethoxy)methyl] -ethane; 1,1,1 tris[(2 hydroxypropoxy)methyl]-propane;and the like, as well as mixtures thereof.

Alternatively the organic polyol starting materials of this inventioncan be mixtures consisting essentially of said above defined polyethertriols and other polyether polyols having an average of at least twohydroxyl groups, said above defined polyether triols amounting to atleast 40 preferably at least 50, weight percent of the total polyolcontent of the mixtures. Illustrative of such other polyethers aretriols outside of the scope defined above, diols, tetraols andpolymer/polyols, and the like, as well as mixtures thereof.

Examples of such polyether polyols that can be mixed with the abovedefined polyether triols include those adducts of alkylene oxide to suchpolyols as diethylene glycol; dipropylene glycol; pentaerythritol;sorbitol; sucrose; lactose; alpha-methylglucoside;alpha-hydroxylalkylglucoside; novolac resins; water; ethylene glycol;propylene glycol; trimethylene glycol; 1,2-butylene glycol;1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,2-hexane glycol;1,10-decanediol; 1,2-cyclohexanediol; 2-butene-l,4- diol;3-cyclohexene-l,l-dimethanol; 4-methyl-3-cyclohexene-1,l-dimethanol;3-methylene-1,5-pentanediol; (2-hydroxyethoxy) 1 propanol;4-(2-hydroxyethoxy)-1-butanol; 5-(2-hydroxypropoxy)-2-octanol;3-allyloxy-1,5- pentanediol; 2-allyloxymethyl 2 methyl-1,3-propanediol;[4,4-pentyloxymethyl] 1,3 propane-diol;3-(o-propenyl-phenoxy)-1,2-propanediol; 2,2 diisopropylidenebisp-phenyleneoxy)-diethanol; and the like, or phosphoric acid;benzenephosphoric acid; polyphosphoric acids such as tripolyphosphoricacid and tetrapolyphosphoric acid; and the like; as well as mixturesthereof.

Another type of polyether polyol that can be mixed with the abovedefined polyether triols and used as the starting materials of thisinvention are graft polymer/ polyether compositions obtained bypolymerizing ethylenically unsaturated monomers in a polyether asdescribed in British Pat. No. 1,063,222 and US. Pat. N01 3,383,351, thedisclosures of which are incorporated here' in by reference thereto.Suitable monomers for producing such compositions include, for example,acrylonitrile, vinyl chloride, styrene, butadiene, vinylidine chloride,and the like. Suitable polyethers for producing such compositionsinclude, for example those polyethers hereinabovedescribed. These graftpolymer/polyether compositions can contain from about 1 to about 70Weight percent, preferably about 5 to about 50 weight percent and mostpreferably about to about 40 Weight percent of the monomer polymerizedin the polyether. Such compositions are conveniently prepared bypolymerizing the monomers in the selected polyether at a temperature of40 to 150 C. in the presence of a free radical polymerization catalyst,such as peroxides, persulfates, percarbonates, perborates and azocompounds as more fully described by the above patent references. Theresulting compositions may contain a small amount of unreactedpolyether, monomer and free polymer as well as the graftpolymer/polyether complex. Especially preferred are the graftpolymer/polyethers obtained from acrylonitrile and polyether triols.

The alkylene oxides employed in producing the preferred polyethersdescribed above normally have from 2 to 4 carbon atoms, inclusive whilepropylene oxide and mixtures of propylene oxide and ethylene oxide areespecially preferred.

The exact organic polyol or polyols employed as the starting materialsof this invention merely depend on the end use of the high resiliencepolyether urethane foam. For instance, the employment of polyethertriols having at least 40 mole percent primary hydroxyl groups andmolecular weights from 2,000 to 8,000 preferably 4,000 to 7,000generally have hydroxyl numbers from 84 to 21, preferably 42 to 28 andgive primarily flexible polyether foams. The supplementary polyetherswhich may have any proportion of primary to secondary hydroxyl groupsand which may be mixed with the required polyether triols can be used tocontrol the degree of softness of the foam or vary the load bearingproperties of the foam. Such limits are not intended to be restrictive,but are merely illustrative of the large number of possible combinationsof polyether triols and other polyethers that can be employed.

The hydroxyl number is defined as the number of milligrams of potassiumhydroxide required for the complete neutralization of the hydrolysisproduct of the fully acetylated derivative prepared from 1 gram ofpolyol or mixtures of polyols with or without other crosslinkingadditives used in the invention. The hydroxyl number can also be definedby the equation:

wherein OH=hydroxyl number of the polyol.

A variety of organic isocyanates can be employed in the foamformulations of this invention for reaction with the organic polyolstarting materials above described to provide high resilience polyetherurethane foams. Preferred isocyanates are polyisocyanates andpolyisothiocyanates of the general formula:

wherein Y is oxygen or sulfur, i is an integer of two or more and Q isan organic radical having the valence of i. For instance, Q can be asubstituted or unsubstituted hydrocarbon radical, such as alkylene andarylene, having one or more aryl-NCY bonds and/or one or more alkyl- NCYbonds. Q can also include radicals such as -QZQ, where Q is an alkyleneor arylene group and Z is a divalent moiety such as -O, OQO, --CO--, COS, --S--Q+, -SO and the like. Examples of such compounds includehexamethyl diisocyanate, 1,8-diisocyanato-p-methane, xylylenediisocyanate, (OCNCH CH 'CH 'OCH O,1-methyl-2,4-diisocyanatocyclohexane, phenylene diisocyanates, tolylenediisocyanates, chlorophenylene diisocyanates,diphenylmethane-4,4'-diisocyanate, naphthalene-1,5 diisocyanate,triphenylmethane-4,4-4"-triisocyanate, andisopropylbenzene-alpha-4-diisocyanate.

Further included among the isocyanates useful in this invention aredimers and trimers of isocyanates and diisocyanates and polymericdiisocyanates such as those having the general formula:

in which i and j are integers of two or more, and/or (as additionalcomponents in the reaction mixtures) compounds of the general formula:

in which i is one or more and L is a monofunctional or polyfunctionalatom or radical. Examples of this type include ethylphosphonicdiisocyanate, C H P(O) (NCO) phenylphosphonic diisocyanate, C H P (O)(NCO) compounds containing a ESi-NCO group, isocyanates derived fromsulfonamides (QSO NCO), cyanic acid, thiocyanic acid, and compoundscontaining a metal -NCO radical such as tributyltinisocyanate.

More specifically, the polyisocyanate component employed in thepolyurethane foams of this invention also includes the followingspecific compounds as well as mixtures of two or more of them:2,4-tolylene diisocyanate, 2,6tolylene diisocyanate, crude tolylenediisocyanate, bis- (4-isocyanatophenyl)methane, polymethylenepolyphenylisocyanates that are produced by phosgenation ofanilineformaldehyde condensation products, dianisidine diisocyanate,toluidine diisocyanate, xylylene diisocyanate, bis(2- isocyanatoethyl-fumarate, bis 2-isocyanatoethyl carbonate,1,6-hexamethylene-diisocyanate, 1,4 tetrarnethylenediisocyanate, 1,10deca-methylene-diisocyanate, cumene- 2,4-diisocyanate, 4methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylenediisocyanate,4 bromo-1,3-phenylene diisocyanate, 4-ethoxy 1,3 phenylene-diisocyanate,2,4-diisocyanata-diphenylether, 5,6 dimethyl-l,3-phenyl enediisocyanate, 2,4-dimethyl-l,3-phenylenediisocyanate,4,4-diisocyanatodiphenylether, bis 5,6-(2 iso cyanatoethyl)bicyc1o[2.2.1]hept-2 ene, benzidinediisocyanate,4,6-dimethyl-l,3-phenylenediisocyanate, 9,10-anthracenediisocyanate,4,4'-diisocyanatodibenzyl, 3,3-dimethyl-4,4'-diisocyanatodiphenylmethane, 2,6-dimethyl-4,4'-diisocyanatodiphenyl,2,4-diisocyanatostilbene, 3,3'-dimethyl-4,4'- diisocyanatodiphenyl,3,3'-dimethoxy-4,4-diisocyanatodi phenyl, 1,4-anthracenediisocyanate,2,5 fluorenediisocyanate, 1,S-naphthalenediisocyanate, 2,6diisocyanatobenzfuran, 2,4,6-toluenetriisocyanate, and many otherorganic polyisocyanates that are known in the art, such as those thatare disclosed in an article by Siefken, Ann., 565, 75 (1949). Ingeneral, the aromatic polyisocyanates are preferred.

Particularly useful isocyanate components of high resilience cold cureformulations within the scope of this invention are combinations ofisomeric tolylene diisocyanates and polymeric isocyanates having unitsof the formula Noo

IARJ.

cyanato groups required to react with all of the hydroxyl groups of theorganic polyol starting materials and with any water present as ablowing agent. Most preferably, a slight amount of isocyanato groups inexcess to the stoichiometric amount is employed.

The blowing agents employed in this invention include methylenechloride, water, liquefied gases which have boiling points below 80 F.and above --60 F., or by other inert gases such as nitrogen, carbondioxide, methane, helium and argon. Suitable liquefied gases includesaturated aliphatic fiuorohydrocarbons which vaporize at or below thetemperature of the foaming mass. Such gases are at least partiallyfiuorinated and can also be otherwise halogenated. Fluorocarbon blowingagents suitable for use in foaming the formulations of this inventioninclude trichloromonofluoromethane, dichlorodifiuoromethane,dichlorofiuoromethane, 1,l-chloro-l-fluoroethane, 1-chloro-1,1-difiuoro, 2,2-dichloroethane, and 1,1,1-trifluoro,2-chloro-2-fluoro, 3,3-difluoro-4,4,4-trifluorobutane. The amount ofblowing agent used will vary with density desired in the foamed product.Usually from 2 to parts by weight of the blowing agent per 100 parts byweight of the organic polyol starting materials are preferred.

The catalysts employed in this invention include any of the catalystused in producing conventional flexible polyurethane foam. Illustrativecatalysts are conventional amine catalysts such as N-methyl morpholine,N-ethyl morpholine, hexadecyl dimethylamine, triethylamine, N,N,N',N'tetramethyl 1,3 butanediamine, N,N- dimethylethanolamine, bis(2dirnethylaminoethyl)ether, N,N,N',N' tetramethylethylenediamine, 4,4methylene bis(2 chloroaniline), dimethyl benzylamine, N coco morpholine,triethylene diamine, [1,4 diazobicyclo (2,2,2)-octane], the formatesalts or triethylene diamine, other salts of triethylene diamine andoxyalkylene adducts of primary and secondary amino groups, and the like.If desired, conventional organo metal catalysts may be used tosupplement the amine catalysts. Illustrative of such metal catalysts arethe tin salts of various carboxylic acids e.g. stannous octoate, dibutyltin dilaurate, nickel acetylacetonates, and the like. Generally thetotal amount of catalyst employed in the mixtures will range from 0.1 to0.5 or 2 weight percent based on the total weight of the organic polyolstarting materials.

The relative amounts of the various components reacted in accordancewith the above described process for producing high resilience polyetherurethane foams in accordance with this invention are not narrowlycritical. The polyether and the polyisocyanate are present in the foamformulations used to produce such foams in major amount. The relativeamounts of these two components is the amount required to produce theurethane structure of the foam and such relative amounts are well knownin the art. The blowing agent, catalyst and surfactants are each presentin a minor amount necessary to achieve the function of the component.Thus, the blowing agent is present in a minor amount sufiicient to foamthe reaction mixture, the catalyst is present in a catalytic amount(i.e., an amount sufficient to catalyze the reaction to produce theurethane at a reasonable rate) and the siloxane oil surfactants arepresent in a foam-stabilizing amount (i.e. in an amount sufficient tostabilize the foam). Preferred amounts of these various components aregiven hereinabove.

The high resilience cold cure urethane foams produced in accordance withthis invention can be used for the same purposes as correspondingconventional hot cure polyether urethane foams, e.g. they can be usedwhere ever cushioning is desired, e.g. in furniture; in transportationsystems, automobiles, planes, etc.; in carpeting; in the packaging ofdelicate objects; and the like.

Other additional ingredients can be employed in minor amounts inproducing the high resilience polyether urethane foams in accordancewith the process of this invention, if desired, for specific purposes.Thus inhibitors (e.g.

d-tartaric acid and tertiary-butyl pyrocatechol, Ionol) can be employedto reduce any tendency of the foam to hydrolytic or oxidativeinstability. Flame retardants (e.g. tris(2 chloroethyl)phosphate) can beused. Dihydrocarbon silicone oils, e.g. dimethylsiloxane and thesiloxaneoxyalkylene block copolymers described in U.S. Application No.84,181 filed Oct. 26, 1970 now U.S. Pat. 3,741,- 917 may be mixed ifdesired with the siloxane oils employed in this invention. While suchmixtures are not required they may help expand the usefulness of thesiloxane oils employed herein by broadening the siloxane oilconcentration range, providing more processing latitude and increasingthe adaptability of the siloxane oil to a variety of foam formulations.Of course any organic solvent for the amine catalysts, e.g. polyols suchas hexylene glycol (i.e. 2 methyl 2,4 pentanediol), diproylene glycol,and the like can be used which substantially do not adversely affect theoperation of the process or reactants. Examples of other additives thatcan be employed are crosslinkers such as glycerol, triethanol amine, andtheir oxyalkylene adducts, and anti-yellowing agents.

An additional feature of the instant invention are the novelcompositions suitable for use in producing the high resilience polyetherurethane foam. For example it may be desirable, particularly on acommercial scale to employ the siloxane oil in a diluted form, i.e. inthe form of a siloxane oil-solvent solution premix or a siloxaneoilsolvent-catalyst solution premix. Such solution premixtures can helpserve to eliminate any mixing, metering, or oil settling problems.Moreover, fewer streams of ingredients may be needed at the mixing headof the operational apparatus. Of considerable importance is that theformulator has the latitude to select the particular solvent which bestsuits the system and minimize or eliminate any loss of foam properties.Siloxane oil-solvent-catalyst premixes can also be used since theselected solvent can be one which serves the dual role of solvent forthe catalysts as well as the siloxane oil. This option of formulating apremix simplifies the foaming operation and improves the precision ofmetering ingredients. While any suitable organic solvent such ashydrocarbon, halo-hydrocarbons, organic hydroxyl compounds, alkylphthalates, and the like may be employed, preferably when employed thesolvent selected should be one in which the aralkyl modified siloxaneoil is substantially soluble. For example, it is preferred that at leastfive parts by weight of the aralkyl modified siloxane oil be soluble inparts by weight of solvent. More preferably the minimum percentage ofaralkyl modified siloxane oil in the siloxane oil-solvent or siloxaneoil-solvent-catalyst solutions should be in the range of at least aboutten to at least about 20 weight percent. Of course it is understood thatsuch solvents need not be employed and that the maximum percentage ofaralkyl modified siloxane oil in said solvent solutions is not critical.Moreover, when employed such solvent solutions should of course becorrelated to the amounts of active aralkyl modified siloxane oil thatmay be employed per hundred parts by weight of the organic polyolstarting material as outlined above. The same correlation should also bemade with regard to catalyst when a siloxane oil-solvent-catalystsolution is employed. Preferably the solvent for the aralkyl modifiedsiloxane oil is an organic hydroxyl compound such as hydroxyl terminatedorganic ether compounds. More preferably they are polyether triols,diols, and monools such as the adducts of ethylene oxide, propyleneoxlde, butylene oxide, with starters such as glycerol, water,trimethylolpropane, 1,2,6-hexanetriol, ethylene glycol, butanol,nonylphenol, and the like. Of course the oxyalkylene units of suchadducts may be of dilferent types, e.g. oxypropylene and oxyethylenegroups, and may be randomly distributed or in blocks. The most preferredsolvents are the polyether triols having all or predominantlyoxypropylene units in the oxyalkylene portion and having molecularweights in the range from about 2,000 to 6,000 inasmuch as they may bethe same, as or similar to the primary triols employed as the organicpolyol starting material of the foam formulation. Moreover thisdiscovery concerning the solubility of the aralkyl modified siloxaneoils of this invention can be regulated and controlled, e.g. atrelatively low molecular weights of these oils, where viscosities are ofthe order of about ten centistokes or less, the moles of dimethylsiloxyunits can substantially exceed the number of moles ofaralkylmethylsiloxy units, inasmuch as the low average molecular weightmakes a contribution towards solubilization. At higher molecularweights, e.g. at viscosities of 30 centistokes or higher, a greaterproportion of aralkylmethylsiloxy units, then used for low molecularweight oils, may be necessary to achieve satisfactory solubility.

In accordance with this invention, the cold cure polyether urethanefoams can be produced by any suitable technique. The preferred processis a one-step or one shot technique wherein all of the reactants arereacted simultaneously with the foaming operation. A second generalprocess is called the prepolymer process whereby a prepolymer is formedby reacting the polyether starting material with a small excess of theisocyanate and later foaming the prepolymer by the reaction with wateror an inert blowing agent. Another method which can be used is thequasi-prepolymer technique which involves reacting a large excess of theisocyanate with the polyether starting material and then subsequentlyfoaming this product with additional polyether in the presence of ablowing agent. Sometimes it is preferred to premix the polyetherstarting material and siloxane oil stabilizer although any suitablepremixture of the various ingredients can be used, e.g. a siloxaneoil-solvent-catalyst solution as outlined above. Of course it isunderstood that the ingredients of the foam forming formulation can bemixed in any suitable manner prior to commencing the cure reaction.Because of the high exothermic nature of the reaction high resilienceurethane foams are rapidly produced without the need of any externalheat by mixing the reactants at ambient temperatures and pouring thefoaming reaction mixture into a suitable mold and allowing the foam tocure itself. Of course, if desired the overall reaction can be evenfurther accelerated by preheating the mold and or employing conventionalhigh temperature post curing procedures. Within a shorter period of timethe cold cure process, with or without post cure, simultaneouslyachieves a greater degree of cure throughout the entire foam, andshorter tack free and demolding time, then is generally achieved withconventional hot cure processes. For instance, cold cure foams can beremoved from the mold far sooner Without substantial damage to thesurface than conventional hot cure foams. Of course it is to beunderstood that the high resilience polyether urethane foams of thisinvention can also be prepared in slabstock form, if desired.

The following examples illustrate the present invention and are not tobe regarded as limitative. It is to be understood that Me" represents amethyl radical, Cone. represents concentration, p.h.p. refers to partsof active siloxane block eopolymer per hundred parts of organic polyolstarting material cstk. C. represents the centistoke viscosity measuredat 25 C., 100 Index indicates that the number of moles of NCO groups isequal to the total moles of hydroxyl groups in the foam formulation, andthat all of the parts, percentages and proportions referred to hereinand in the appended claims are by weight unless otherwise indicated.

EXAMPLE 1 Into a flask equipped with a condenser, stirrer andthermometer where charged about 81 grains (0.50 mole) ofhexamethyldisiloxane and about 318 grams of aphenylethylmethylsiloxane-methylsiloxane hydrolyzate having a viscosityof about 400 centistokes at 25 C. and consisting of about 4.9 grams(0.029 mole) of trimethylsiloxy end-blocker, about 164 grams (1.0 mole)of phenethylmethylsiloxy groups and about 149 grams (2.0 mole) ofdimethylsiloxy groups. The mixture was then equilibrated under anitrogen blanket by adding about 0.7 grams (70 drops) oftrifluoromethane sulfonic acid catalyst and stirring for about 2 hoursat C. The equilibrate was neutralized with sodium bicarbonate andfiltered. There was obtained a colorless phenylethyl-modified siloxaneoil product having a viscosity of about 11 centistokes at 25 C. Saidproduct siloxane is hereinafter referred to as Siloxane I and itsaverage composition and formula are given in Tables 1 and 2 below.

EXAMPLE 2 Example 1 was repeated using about 49.2 grams ofhexamethyldisiloxane and about 150.8 grams of thephenylethylmethylsiloxane methylsiloxane hydrolyzate. There was obtaineda colorless phenylethyl-modified siloxane oil product having a viscosityof about 8 centistokes at 25 C. Said product siloxane is hereinafterreferred to as Siloxane II and its average composition and formula aregiven in Tables 1 and 2 below.

EXAMPLE 3 Example 1 was repeated using about 157 grams ofhexamethyldisiloxane, about 343 grams of thephenylethylmethylsiloxane-methylsiloxane hydrolyzate, about 0.2 grams(20 drops) of the trifluoromethane sulfonic acid catalyst and thereaction maintained at 7080 C. for about 2 hours. The neutralized,filtered siloxane was sparged with nitrogen at 160 C. for about 2 hoursand about 98 cc.s of lites recovered. About 330 grams of a colorlessphenylethyl-modified siloxane oil product having a viscosity of about 13centistokes at 25 C. was obtained. Said product siloxane is hereinafterreferred to as Siloxane III and its average composition and formulabefore sparging are given in Tables 1 and 2 below.

EXAMPLE 4 Example 3 was repeated using about 77 grams ofhexamethyldisilo-xane, about 298 grams of the phenylethyl'methylsiloxane-methylsiloxane hydrolyzate, along with sparging theneutralized, filtered siloxane at 160 C. for about 2-3 hours. There wasobtained a colorless phenylethyl-modified siloxane oil product having aviscosity of about 18 centistokes at 25 C. Said product siloxane ishereinafter referred to as Siloxane IV and its average composition andformula before sparging are given in Tables 1 and 2 below.

EXAMPLE 5 Example 3 was repeated using about 75 grams ofhexamethyldisiloxane, about 298 grams of thephenylethylmethylsiloxane-methylsiloxane hydrolyzate, about 0.45 grams(45 drops) of the trifluoromethane sulfonic acid catalyst, along withsparging the neutralized, filtered siloxane at 160 C. for about 3 hours.There was ob tained a colorless phenylethyl-modified siloxane oilproduct having a viscosity of about 27 centistokes at 25 C. Said productsiloxane is hereinafter referred to as Siloxane V and its averagecomposition and formula before sparging are given in Tables 1 and 2below.

EXAMPLE 6 A mixture of about 41.9 grams of a Me SiO(Me SiO) (HSiMeO)SiMe siloxane having a viscosity of about 3.5 centistokes at 25 C.,about 33.1 grams of alpha-methylstyrene and about 0.038 grams of Ionol,an inhibitor was prepared and heated to 70 C. Then about 7 drops of asolution consisting of 3 parts by weight of H PtCl -6H O, 15 parts byweight of ethanol and 82 parts by Weight of glycidyl glycoldimethylether was added so as to furnish about 25 parts of platinum permillion parts of the reactants employed. An exotherm to 115 C. wasobserved and the reaction maintained at about C. until completed. The

1 1 siloxane was then neutralized with sodium bicarbonate, sparged withnitrogen at 130 C. (about 11 cc.s of lites were recovered) and filtered.There was obtained a colorless phenylisopropyl-modified siloxane oilproduct having a viscosity of about 35 centistokes at 25 C. Said productsiloxane is hereinafter referred to as Siloxane VI and its averagecomposition and formula before sparging are given in Tables 1 and 2below.

EXAMPLE 7 Example 1 was repeated using about 25.4 grams ofhexamethyldisiloxane, about 51 grams of thephenylethylmethylsiloxane-methylsiloxane hydrolyzate, about 23.6 gramsof a mixture of tri and tetra dimethylcyclic siloxane, and about 0.09grams (9 drops) of the trifluoromethane sulfonic acid catalyst. Therewas obtained a colorless phenylethyl-modified siloxane oil producthaving a viscosity of about 7 centistokes at 25 C. Said product siloxaneis hereinafter referred to as Siloxane VII and its average compositionand formula are given in Tables 1 and 2 below.

EXAMPLE 8 Example 1 was repeated using about 4.4 grams ofhexamethyldisiloxane, about 7.3 grams of tetracyclicphenylisopropyl(methyl) siloxane, about 33.3 grams of thephenylethylmethylsiloxane methylsiloxane hydrolyzate, about 0.05 grams(5 drops) of the trifluoromethane sulfonic acid catalyst and thereaction maintained at 80-85 C. for about 2 hours. There was obtained acolorless phenyl isopropyl-modified phenylethyl-modified siloxane oilproduct having a viscosity of about 36 centistokes at 25 C. Said productsiloxane is hereinafter referred to as Siloxane VIII and its averagecomposition and formula are given in Tables 1 and 2 below.

EXAMPLE 9 A mixture of about 30.1 grams of a Me HSiO(Me SiO) SiMe Hsloxane, about 19.9 grams of alpha-methylstyrene, about 0.05 grams ofIonol, one drop of acetic acid and about 9 drops of a solutionconsisting of 3 parts by weight of H PtCl -6H O, 15 parts by weight ofethanol and 82 parts by weight of glycidyl glycol dimethylether so as tofurnish about 50 parts of platinum per million parts of the reactantsemployed was prepared and heated to 110 C. and maintained until thereaction was completed. Then the siloxane was neutralized with sodiumbicarbonate, cooled and filtered. There was obtained a colorlessphenylisopropyl-modified siloxane oil product having a viscosity ofabout 7 centistokes at 25 C. Said product siloxane is hereinafterreferred to as Siloxane IX and its average composition and formula aregiven in Tables 1 and 2 below.

EXAMPLE 10 Example 9 was repeated using about 27 grams of a Me HSiO(MeSiO) SiMe H siloxane and about 22.2 grams of alphamethylstyrene. Therewas obtained a colorless phenylisopropyl-modified siloxane oil producthaving a viscosity of about 6 centistokes at 25 C. Said product siloxaneis hereinafter referred to as Siloxane X and its average composition andformula are given in Tables 1 and 2 below.

EXAMPLE 11 Example 1 was repeated using about 73.1 grams ofhexamethyldisiloxane, about 126.9 grams of thephenylethylmethylsiloxanemethylsiloxane hydrolyzate and about 0.25 grams(25 drops) of the trifiuoromethane catalyst. There was obtained acolorless phenylethyl-modified siloxane oil product having a viscosityof about 4.2 centistokes at 25 C. Said siloxane product is hereinafterreferred to as Siloxane XI and its average composition and formula aregiven in Tables 1 and 2 below.

Siloxanes I to XI were compared with five other siloxane oils,hereinafter referred to as Siloxanes A to E, the average composition andformula of distilled Siloxane A, as well as the average compositions andformulas of Siloxanes B to E before sparging also being reported inTables 1 and 2 below.

Viscosity Siloxane (1 (cs. 25 C.)

Average composition of dimethyl siloxane oils A Me 0 8 0 0 B Me 0 11 0 0TABLE 2.AVERAGE FORMULA FOR ARALKYL-MODIFIED SILOXANE OILS SiloxaneTABLE 2-Continued Siloxane VIII [(QCHMeCHP) (Me) S101 s 1M0;

CHMeCHr Mei s10 (Me: s10)... s 1M9. (-cmmon-Q) CHMeOHz Mez s 10 (Mei s10s iMei(-c11,MeoH-) Me:SlO(MezS10) .s[( CzH4-) (Me) SlO]o oSlMe1 M93810(MeiSiOhm CaHi- (Me) Si] .|SiMe;

Me:SiO(MezS)n.7[ C2Hl) (Me) S 1015 .uSlMe;

Average formula for dimethyl siloxane oils A M93810 (MezSlOhSlMGa t0Measlo (M62310) oSlMea, inclusive. B MesSiO (MezSiOhSiMe; t0 M63510(MBzSlOMeSlMes, inclusive.

O omposition Designation Organic polyols:

E1 This is a polyether triol, mol. wt. about 6,000; hydroxyl No. about27; containing about 85 mole percent primary hydroxyl groups produced byreacting about 89% propylene oxide and about 11% ethylene oxide withglycerol.

E2 This is a polyether triol, moi. wt. about 5,000; hydroxyl No. about34; containing about 75 mole percent primary hydroxyl groups produced byreacting about 84% propylene oxide and about 16% ethylene oxide withglycerol.

E3 This is a graft polymerlpolyol; about 80 wt. percent polyol, 10 wt.percent styrene and 10 wt. percent acryionitrile; having a hydroxyl No.of about 28, produced by polymerizing styrene and acrylonitrile in E2.

Polyisocyanates:

C1 This is a mixture oi. about 80 wt. percent 2,4-

tolylene diisocyanate and about 20 wt. percent 2.6-toluene diisocyanate.

C2 This is a polymethylene polyphenyl isocyanate polymer containingabout 2.6-2.9 moles of N00 per mole of polymer and having an isocyanatecontent of about 31.4%.

c3 This is a composition of about 80 wt. percent 01 and about 20 wt.percent C2. C4 This is a blend of 1 part by wt. of C1 and 1 art by wt.of the isocyanate polymeric residue having an amine equivalent No. ofabout 106, of the production of C1. Catalyst:

This is a composition consisting 0! about 70 wt. percent bis(N,N-dimethylaminoethyl) ether and about wt. percent dipropylene glycolsolvent.

A2 This is a composition consisting of about 33 wt.

percent triethylenediamine and about 67 wt.

percent dipropylene glycol solvent.

Siloxane oil solvents:

S1 This is a polyether triol, mol. wt. about 3700; hydroxyi No. about46, containing about 0-5 mole percent primary hydroxyl groups and havingsome internal oxyethylene units, produced by reacting 14% ethylene oxideand 86% propylene oxide with glycerol.

This is a polyether triol, mol. wt. about 3,000 produced by reactingpropylene oxide with glycerol. S3 Polyether trlol E2.

EXAMPLE 12 The foam formulations employed in producing the foams in thisexample were identical save for variations in the amount of activearalkyl modified siloxane oil employed. The high resilience polyetherurethane foams were prepared by adding the final mixture of foam formingingredients to an uncovered mold and allowing the formulations to cure.Thereafter the foam containing mold was placed in an oven at 125 C. forabout 2 minutes to facilitate separation of the paper liner from themold. Said formulations contained 100 parts by weight of organic polyolson the order of about 50 parts of polyether triol El and about 50 partsof polyether triol E3; about 2.8 parts by weight of water; about 0.08parts by weight of amine catalyst A1; about 0.8 parts by weight ofN-ethylmorpholine catalyst; about 0.08 parts by weight of solidtriethylene diamine catalyst; about 0.015 parts by weight ofdibutyltindilaurate catalyst and about 34.9 parts by Weight ofpolyisocyanate C3 (100 Index). The aralkyl modified siloxane oil wasused in the form of a siloxane oil-solvent solution composed of aboutparts by weight of solvent S1 and about 10 parts by weight of siloxaneoil, Siloxane I. The active amount of siloxane oil used was varied andthe results are reported in the following table.

TABLE 4 Acti siloxane Cells Foa conc per Shrlnk- No Siloxane oil(p.h.p.) inch age Cellunlformiiy one 10 None Severe voids- (control).irregular.

0.15 45 do-. Uniform-No.

voids. 0.10 41 do.. Do. 0.075 35 do Do. 0.05 31 o. D0.

EXAMPLE 13 Another series of high resilience polyether urethane foamswas produced in the same manner as Example 12 using the same foamformulation except that Siloxane II was substituted for Siloxane I inthe solvent solution. The results are reported in the following table.

15 EXAMPLE 14 High resilience polyether urethane foams were produced inthe same manner as Example 12, using formulations containing 100 partsby weight of polyether triol E2; about 3.2 parts by weight of water;about 7.0 parts by weight of triethanolarnine; about 1.5 parts by weightof amine catalyst A2; about 53.1 parts by weight of polyisocyanate C4(100 Index). The siloxane oil employed was not used in the form of asolvent solution; the solvent for the siloxane oil being omitted. Thesiloxane oil employed and the results obtained are reported in thefollowing table.

A series of comparative high resilience polyether urethane foams wasproduced in the same manner as Example 12, using the same foamformulation, except that the siloxane oils employed were not used in theform of solvent solution, the solvent for the siloxane oil beingomitted. The amount and nature of the siloxane oil was varied asreported in the following table.

16 EXAMPLE 17 This example illustrates the superior solubility ofSi-loxane 11 over siloxane oils not of this invention in various solventsolutions. The results of the blends are reported in the followingtable.

TABLE 9 Wt. Wt. percent percent Solsiloxane solvent Appearance ofSiloxane oil vent in blend in blend blend 10 90 Clear. 10 90 D0. 10 90Do.

3 97 Slightly turbid. 3 97 Very turbid. 3 97 Do.

1 Siloxane not of this invention.

EXAMPLE 18 TAB LE 7 Active siloxane siloxane Cells viscosity eonc. perFoam No. Siloxane oil (es. 25 C.) (p.h.p.) inch Shrinkage Celluniformity 1 None (control) 10 None Severe voids-irregular.

siloxane oils for this invention 2 siloxane I 11 0. 1 41 .....doUniform-n voids. R Siloxane TI 8 0. 1 Do. 4 Siloxane 13 0. 1 Do. 5siloxane IV 18 0. 1 Do. 6 Siloxane V 27 0. 075 Do. 7 siloxane VI 35 0.04Do. R Siloxane 4. 2 0. 1 D0.

Siloxane oils not or this invention 7 0. 05 35 Moderate-mo voids 7 0. 1046 Moderate-no voids 57 0. 05 Severe 44 0. 05 Severe 47 0. 05 42Moderate-no voids Too much shrinkage for cell count.

EXAMPLE 16 A series of comparative siloxane oil-organic solventsolutions were prepared by blending various amounts of siloxane oil inpolyether solvent S2 to determine the solubility of the siloxane oil.The results are reported in the following table.

TABLE 8 Solvent solution Wt. Wt. percent percent polyether Siloxanesiloxane trlol 82 Appearance viscosity Siloxane oil in blend in blend ofblend (cs. C.)

Siloxanes of this invention:'

siloxane I.... 5 11 20 11 Biloxane II- 20 8 Siloxane III 5 13 SiloxaneIV... 5 18 siloxane V... 5 27 Siloxane VI..- 5 siloxane VII 5 7 SiloxaneVIII. 10 36 Siloxane IX 20 7 Siloxane X 2O 6 Siloxanes not oi thisinvention:

siloxane A 3 97 Slightly turbid 5 Siloxane A 5 95 Very turbid 5 siloxaneB l 1 d 7 Siloxane C 5 5 57 Siloxane D 5 5 .do. 44 siloxane E.... 5 5Slightly turbld 47 Not maximum selubllities for Siloxanes I through X.

active amount of siloxane oil was also varied and the results obtainedare reported in the following table.

The above data in Examples 12 to 15 and 18 demonstrate that theirregular cell structure and voids of the control foams can beeliminated by employing the siloxane oil stabilizers of this inventionwithout causing any foam shrinkage. Moreover the above data in Example15 demonstrates that while the use of siloxane oils not of thisinvention helped eliminate the voids of the control foam, they alsocaused moderate or severe foam shrink-age and therefore are not usefulas stabilizers in the production of high resilience polyether urethanefoam. In cases of moderate foam shrinkage the normally smooth regularcrown is substantially puckered and wrinkled. This surface shrinkage isrelated to an abnormal quantity of closed cells and tight foam which inturn adversely effects the foams properties such as its resiliency,compression set and load bearing. In cases of severe shrinkage the abovedefects and disadvantages are even more aggravated and pronounced. Inaddition severe shrinkage is further evidenced by a pulling away of thefoam from the sides and/or bottom of the mold.

The data in Examples 16 and 17 demonstrate that the siloxane oils ofthis invention are highly soluble in various organic solvents, whichsiloxane oils not of this invention are only slightly soluble in thesame solvents. Thus it is obvious that reasonable amounts of solventsolutions of the siloxane oils of this invention can be employed in theproduction of high resilience polyether urethane foams, whereas notenough of the silixone oils, not of this invention, can be dissolved inthe same solvents to provide for stabilization at practicle solutionconcentrations in the production of said foams.

Various modifications and variations of this invention will be obviousto a worker skilled in the art and it is to be understood that suchmodifications and variations are to be included within the purview ofthis application and the spirit and scope of the appended claims.

What is claimed is:

1. An aralkyl modified siloxane oil having the average formula wherein xhas a value of 2 to 8 inclusive; y has a value of to 6 inclusive; 2 hasa value of 0 to 1 inclusive; R is a lower alkyl or phenyl radical; and Xis an aralkyl radical of the formula where a has a value of 2 or 3; saidsiloxane containing at least one of said aralkyl radicals and having aviscosity in the range of about 4 to about 40 centistokes at 25 C.

2. A siloxane oil as defined in claim 1 having a viscosity in the rangeof about 5 to about 20 centistokes at 25 C.

3. A siloxane oil as defined in claim 1 wherein z is 0 and R is a loweralkyl radical.

4. A siloxane oil as defined in claim 3 wherein R is a methyl radical,and X is 8. A siloxane oil as defined in claim 1 having the averageformula MeaSiO (Mansion-Me S1O)1.9SiMe;

wherein Me is a methyl radical.

9. A siloxane oil as defined in claim 1 having the average formulaMeaSlO (MezSlO)3.g(MeSiO)i.5SiMea wherein Me is a methyl radical.

10. A siloxane oil as defined in claim 1 having the average formulaMeasio(M81SiO)1.s(MoSiO)o.uSiMea wherein Me is a methyl radical.

11. A siloxane oil as defined in claim 1 having the average formulawherein Me is a methyl radical.

12. A siloxane oil as defined in claim 1 having the average formula (Q0HM8CH1) (M87) SiO (MegSiO) .oSi(Meg) (CHzMeCH--) wherein Me is a methylradical.

13. A siloxane oil as defined in claim 1 having the average formula(Q-Qmawm) M6,) SiO (MezSiOhSKMm) (madman-Q) wherein Me is a methylradical.

14. A siloxane oil as defined in claim 1 having the average formulawherein Me is a methyl radical.

US. Cl. X.R.

25249.6, 78; 260-25 AH, 448.2 R

lnvjentofls) E3?- Morehonse UNITED STATES YPATENT @FFIQE @IIWQATE @Feoho ow Patent No. 3,839, 384 Dated v I Itis certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column, 6, line 60 "N65" ehould read ammo-J1.

Column 8, line 16, d1 proylene" should read ---dipropyleno---.

Column 12, TABLE 2 in the formula of Siloxane III after the last bracket"1A" should read "1.1";

' Columnqlg TABLE 2, in the formula of Siloxane IV after "8:10) 3.0"should read --3.8--.

Column 17, line 9, "which" should read --while-.

Signed and'sealed this 18th day of February-1975.

(SEAL) Attest: I

Cu MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officerand Trademarks,

2 (149) uscoMM-Dc 60376-P69 9 1.5. GQVERNNENT PRNTING OFFICE \990-355-334.

1. AN ARALKYL MODIFIED SILOXANE OIL HAVING THE AVERAGE FORMULA